Work

The intramolecular Diels–Alder reaction of tryptamine-derived Zincke aldehydes is a stepwise process

Year: 2012

Type: article

Abstract: Computational studies show that the base-mediated intramolecular Diels-Alder of tryptamine-derived Zincke aldehydes, used as a key step in the synthesis of the Strychnos alkaloids norfluorocurarine and strychnine, proceeds via a stepwise pathway. The experimentally determined importance of a potassium counterion in the base is explained by its ability to preorganize the Zincke aldehyde diene in an s-cis conformation suitable to bicyclization. Computation also supports the thermodynamic importance of the generation of a stable enolate in the final reaction step. The thermal cycloreversion reaction of the Diels-Alder products is also found to proceed in a stepwise manner.

Source: Chemical Science

DOI: 10.1039/c2sc01072k

Authors: Hung V. Pham, David B. C. Martin, Christopher D. Vanderwal, K. N. Houk

Institutions: University of California, Los Angeles, University of California, Irvine

Language: English

Topic: Organic Chemistry Cycloaddition Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Awards: G1515617636, G363700809, Stereoselectivities of Synthetic Organic Reactions, G5613303288